The utility of mitomycin C in cancer chemotherapy has been limited by its toxic side effects. An objective of this project is to develop chemical methods to synthesize new mitomycin analogues for evaluation as antitumor agents. Target compounds include C-homo mitosenes, 1,2-aziridino mitosenes, and pyrroloindolines bearing the characteristic 9a-oxy group of the mitomycins with or without additional substitution at positions 1,2,9 and 10. Another aspect of this research is the development of new synthetic methodology based on nitrones or their tautomers, N-vinylhydroxylamines. Procedures for intramolecular alpha-functionalization via [3,3]- and [2,3] sigmatropic rearrangements of N-vinylhydroxylamine derivatives are to be explored. Nitrones of esters (alpha-oxy-nitrones and alpha-thionitrones) are to be prepared and their alpha-functionalizing rearrangements and cycloaddition reactions will be studied. The use of N-chiral nitrones for asymmetric alpha-functionalization and for the preparation of chiral amines by stereo-selective addition of carbon nucleophiles is proposed.